Separation of gases via carbonized vinylidene chloride copolymer gas separation membranes and processes therefor

ABSTRACT

A carbonized PVDC copolymer useful for the separation of an olefin from its corresponding paraffin may be made by heating a polyvinylidene chloride copolymer film or hollow fiber having a thickness of 1 micrometer to 20 micrometers to a pretreatment temperature of 100° C. to 180° C. to form a pretreated polyvinylidene chloride copolymer film and then heating the pretreated polyvinylidene chloride copolymer film to a maximum pyrolysis temperature from 350° C. to 750° C. A process for separating an olefin from its corresponding paraffin in a gas mixture is comprised of flowing the gas mixture through the aforementioned carbonized polyvinylidene chloride (PVDC) copolymer to produce a permeate first stream having an increased concentration of the olefin and a second retentate stream having an increased concentration of its corresponding paraffin.

The present invention relates to the field of gas separation using a carbon membrane. More particularly, it relates to the separation of gases and in particular olefins from their corresponding paraffins from a gas mixture by passing the gas mixture through a carbonized vinylidene chloride copolymer membrane (film or hollow fiber).

Carbon molecular sieves (CMS) and CMS membranes have been used to separate gases. CMSs may be prepared from a variety of resins that are pyrolyzed at various temperatures and/or under various conditions. The pyrolysis reduces the resins to carbon, but maintains at least some porosity, in the form of micropores, in the pyrolyzed product. The CMSs thus formed may then be employed in conventional gas separations equipment employing adsorption of particular gases, such as packed beds, columns, and the like, where the micropore size determines which gas in a gas mixture is adsorbed and which is not. Adsorption and desorption techniques may be alternated to carry out the separation, according to, for example, conventional pressure swing or temperature swing adsorption methods. CMS membranes have also been used to separate gases by flowing gas mixtures through the CMS membranes.

However, there is a particular challenge in the art to prepare CMSs having micropores of the correct size(s) for certain particular separations. Since the use of CMSs to accomplish separations assumes that the micropores are at least as large as, or larger than, the specified molecule that will enter the micropores, it is necessary to know the “size” of the molecule. Different ways to determine that molecular size have been developed. One commonly employed approach has been to determine a given molecule's “kinetic diameter.” A reference listing a variety of these kinetic diameters, based upon their use in zeolite applications, is D. W. Breck, Zeolite Molecular Sieves: Structure, Chemistry and Use, John Wiley & Sons, Inc. (New York, N.Y. 1974), 636, and these determinations are frequently used even with respect to non-zeolite, carbon molecular sieves that are known to have slit-shaped pores. In view of the above and for purposes hereof, then, the following kinetic diameters, taken from the Breck reference cited supra, are used herein as the representative molecular diameters for the following molecules: He (2.6 Angstroms, Å), H₂ (2.89 Å), N₂ (3.64 Å), CO₂ (3.3 Å), CH₄ (3.8 Å), C₂H₄ (3.9 Å), C₃H₈ (4.3 Å), i-C₄H₁₀ (5.0 Å), SF₆ (sulfur hexafluoride) (5.5 Å), and i-C₈H₁₈ (iso-octane) (6.2 Å). However, because that reference table lacks a kinetic diameter for ethane, and the kinetic diameter given therein for propylene is believed by at least some researchers to be inaccurate for CMS materials per se, the Lennard-Jones collision diameters are used herein, instead of the Breck kinetic diameters, for those two materials. These Lennard-Jones collision diameters are, respectively, C₂H₆ (4.1 Å), and C₃H₆ (4.0 Å). See, for example, Staudt-Bickel C., Koros W. J., “Olefin/paraffin gas separations with 6FDA-based polyimide membranes,” J. Membr. Sci. (2000) 170 (2), 205-214 for further discussion. The kinetic diameters and Lennard-Jones collision diameters are referred to together as “representative molecular diameters.”

Polyvinylidine chloride (PVDC) copolymers have been pyrolyzed to form carbon molecular sieves, but they have tended to form larger pores. Lamond T. G., et al., “6 Å molecular sieve properties of SARAN-type carbons,” Carbon (1965) 3, 59-63. This article describes preparation of a CMS, from a polyvinylidene chloride (PVDC) copolymer, that rejects neopentane (6.0 Å) molecules, but adsorbs smaller molecules, such as, in non-limiting example, CO₂, butane, and iso-butane, non-selectively. In view of this the authors of that article concluded that their CMS had 6 Å micropores.

Another example is disclosed in T. A. Centeno., et al., “Molecular sieve gas separation membranes based on poly(vinylidene chloride-co-vinyl chloride),” Carbon (2000) 38, 1067-1073. This article describes preparation of a composite carbon membrane using the aforesaid material. The membrane is formed with a thin microporous carbon layer (thickness of 0.8 micrometers, μm) obtained by pyrolysis of the polymeric film, supported over a macroporous carbon substrate (pore size 1 μm; macroporosity 30 percent, %). Single gas permeation experiments include helium (He), CO₂, oxygen (O₂), nitrogen (N₂) and methane (CH₄). Selectivities are described as particularly high for O₂/N₂ systems, i.e., a selectivity of about 14 at 25 degrees Celsius (° C.). From this information it can be inferred that the micropore size falls somewhere in a range from the representative molecular diameter of 02 (3.46 Å) to that of N₂ (3.64 Å). This CMS membrane is prepared by pre-treating the supported film at 200° C., a temperature at which the PVDC copolymer precursor is melted before carbonization. The fact that melting is required means that the disclosed CMS structures cannot be prepared in unsupported forms.

In other research, including for example, Laredo G. C., Meneses E., Castillo J., Marroquin J. O., Jimeenez-Cruz F., “Adsorption equilibrium and kinetics of branched octane isomers on a polyvinylidene chloride-based carbon molecular sieve,” Energy Fuels (2008) 22 (4) 2641-2648, polyvinylidene chloride copolymer-based CMSs have been prepared that exhibit relatively large micropore sizes and pore volumes that are suitable for separation of correspondingly large molecules, i.e., those having a representative molecular diameter greater than 5.0 Å.

More recently, WO/2016/003680 described forming a CMS from PVDC copolymers using a two-step pyrolysis at high temperatures from 800° C. to 1700° C. The CMS formed had an average pore size in the range of 3 Å to 5 Å. These CMS were described as being useful for separating Propylene (C₃H₆) and propane (C₃H₈); carbon dioxide (CO₂) and nitrogen (N₂); N₂ and methane (CH₄); ethylene (C₂H₄) and ethane (C₂H₆); and n-butane (C₄H₁₀) and i-butane (C₄H₁₀).

CMS membranes formed from PVDC copolymers have also been made, but they have suffered from low or reverse (rejection of hydrogen with presence of hydrocarbons) hydrogen selectivity as described by M. B. Rao and S. Sircar in J. Membrane Science, 85 (1993) 253-264; T. A. Centeno and A. B Fuertes in Carbon, 38 (2000) 1067-1073 and K. Zhang and J. D. Way in J. Membrane Science 369(2011)243-249.

The gas permeation properties of a membrane can be determined by gas permeation experiments. Two intrinsic properties have utility in evaluating separation performance of a membrane material: its “permeability,” a measure of the membrane's intrinsic productivity; and its “selectivity,” a measure of the membrane's separation efficiency. One typically determines “permeability” in Barrer (1 Barrer=10⁻¹⁰ [cm³ (STP) cm]/[cm² s cmHg], calculated as the flux (n_(i)) divided by the partial pressure difference between the membrane upstream and downstream (Δp_(i)), and multiplied by the thickness of the membrane (l).

$P_{i} = \frac{n_{i}\mspace{14mu} l}{\Delta\; p_{i}}$

Another term, “permeance,” is defined herein as productivity of the membrane or hollow fiber membranes and is typically measured in Gas Permeation Units (GPU) (1 GPU=10⁻⁶ [cm³ (STP)]/[cm² s cmHg]), determined by dividing permeability by effective membrane separation layer thickness.

$\left( \frac{P_{i}}{l} \right) = \frac{n_{i}}{\Delta\; p_{i}}$

Finally, “selectivity” is defined herein as the ratio of one gas's permeability through the membrane or permeance relative to the same property of another gas. It is measured as a unitless ratio.

$\propto_{i\text{/}j}{= {\frac{P_{i}}{P_{j}} = \frac{\left( {P_{i}\text{/}l} \right)}{\left( {P_{j}\text{/}l} \right)}}}$

Thus, it would be desirable to realize a CMS membrane and process to make the CMS membrane from PVDC that would be useful in separating olefins from the corresponding paraffins from gas mixtures such as those encountered in syngas, gases generated in oil refineries, natural gas and olefin cracker gas streams. It would be particularly desirable to provide a PVDC CMS that is in the form of an un-supported membrane or hollow fiber.

-   -   One aspect of the invention is a method of making a carbonized         polyvinylidene chloride copolymer useful to separate an olefin         from its corresponding paraffin comprising,     -   (a) providing a polyvinylidene chloride copolymer film or hollow         fiber having a thickness of 1 micrometer to 20 micrometers,     -   (b) heating the polyvinylidene chloride copolymer film to a         pretreatment temperature of 100° C. to 180° C. to form a         pretreated polyvinylidene chloride copolymer film, and     -   (c) heating the pretreated polyvinylidene chloride copolymer         film to a maximum pyrolysis temperature from 350° C. to 750° C.     -   A second aspect of the invention is a process for separating an         olefin from a gas mixture having the olefin's corresponding         paraffin, the method comprising         -   (i) providing the carbonized polyvinylidene chloride             copolymer membrane of any one of the preceding Claims and         -   (ii) flowing the gas mixture through said carbonized             polyvinylidene chloride copolymer membrane to produce a             permeate first stream having an increased concentration of             the olefin and a second retentate stream having an increased             concentration of its corresponding paraffin.     -   It has been discovered that the separation of olefins (e.g.,         ethylene and propylene) from their corresponding paraffins         (e.g., ethane and propane), may be achieved by flowing these         gases through carbon films made by the aforementioned process,         but only when the film is particularly thin. It is unknown why,         but without being limiting in any way, it is believed that the         particular process may realize an asymmetric microstructure         across the film thickness where there may be large pores at the         surface of the film and a narrow band within the film that has a         smaller pore size. It has been discovered that the thickness is         critical. This may be due to how the HCl evolves when forming         the carbonized PVDC. The performance of the film which may be         due to a particular assymetry may be a result of varying         localized atmospheres during the pre-treatment and pyrolysis         (e.g., partial pressure of HCl), which may be due to the         thickness of the films, restraining of the films or combinations         thereof. The thickness of the film should be at least 1         micrometer thick to 20 micrometers thick. If the thickness is         less than 1 micrometer the separation or integrity of the film         tends to insufficient. If the thickness is greater than about 20         micrometers the permeance suffers. Desirably, the thickness is         from about 2 or 5 micrometers to 15 or 12 micrometers.

The PVDC CMSs of the invention may be prepared from a vinylidene chloride copolymer, comprising a vinylidene chloride monomer and at least one additional comonomer. The comonomer may be selected from a variety of materials, including in particular embodiments a vinyl monomer, vinyl chloride monomer, an acrylate monomer, a methacrylate monomer, a styrenic monomer, acrylonitrile, methacrylonitrile, itaconic acid, chlorotrifluoroethylene, and combinations thereof. In more particular embodiments examples of the vinyl monomers include vinyl chloride, vinyl acetate, acrylonitrile, and combinations thereof. More particular examples of the acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, and combinations thereof. More particular examples of methacrylate monomers include methyl methacrylate, butyl methacrylate, and combinations thereof. A more particular example of styrenic monomers is styrene itself.

In proportion it is preferred that the vinylidene chloride based copolymer, which is herein termed a polyvinylidene copolymer (PVDC), includes at least 60 wt % of vinylidene chloride, based on total weight of the copolymer, and in more preferred embodiments at least 70 wt %. However, it is further desired that the PVDC contains a maximum of 97 wt % vinylidene chloride, and thus preferably contains a minimum of at least 3 wt % of the comonomer or comonomer combination; more preferably from 3 wt % to 40 wt %; still more preferably from 3 wt % to 30 wt %; and most preferably from 3 wt % to 20 wt %.

Particular embodiments of PVDCs that are suitable for use in the invention are those including as a comonomer an acrylate, such as methyl acrylate, ethyl acrylate, butyl acrylate, or a combination thereof, in an amount from 3 wt % to 20 wt %, based on the weight of the PVDC as a whole; more preferably from 3.5 wt % to 15 wt %; and most preferably from 4 wt % to 12 wt %. Another particular embodiment is a PVDC including vinyl chloride in an amount from 3 wt % to 30 wt %; more preferably from 7 wt % to 28 wt %; and most preferably from 9 wt % to 25 wt %.

It is also preferred that the overall weight average molecular weight (Mw) of the PVDC copolymer ranges from 10,000 to 250,000; more preferably from 50,000 to 200,000; and most preferably from 60,000 to 150,000.

Use of additives in the PVDC is also contemplated as being within the scope of the invention. Common additives may include, but are not necessarily limited to, epoxidized oil stabilizers such as epoxidized soybean oil, epoxidized linseed oil, and the diglycidyl ether of bisphenol A. Also frequently employed are liquid plasticizers such as aliphatic and aromatic esters, including for example dibutyl sebacate, acetyl tributyl citrate, dioctyl phthalate, and the like, and combinations thereof. Other common additives may include lubricants, such as polyethylene wax, paraffin wax, oxidized polyethylene wax, and combinations thereof. Lubricants may optionally be included, and may comprise, for example, high density polyethylene, acrylate copolymers and silicone polymers, and combinations thereof. Another group of additives that may be included are acid scavengers such as epoxy compounds, magnesium hydroxide, magnesium oxide, tetrasodium pyrophosphate, calcium phosphate, magnesium phosphate, DHT 4A (a synthetic hydrotalcite-like halogen scavenger available from Kyowa Chemical Industry), calcium oxide, calcium carbonate, and combinations thereof. Antioxidants such as phenolics may also be incorporated. Combinations of any or all of these types of additives may be included in the PVDC.

In proportion, it is preferred that the total amount of all additives combined be no more than 15 wt %, and more preferably no more than 8 wt % or 3 wt %. In many applications, however, an amount of all additives combined of at least 2 wt % may be typical, with use thereof therefore ranging preferably from 2 wt % to 8 wt %, and more preferably from 2 wt % to 3 wt %. Those skilled in the art will be aware of the use of such additives and their indications and contraindications without further direction herein.

Those skilled in the art will also be aware of a variety of means and methods for preparing copolymers. However, in general any of the typical or conventional methods of polymerization, including but not limited to mass polymerization, suspension polymerization, and emulsion polymerization, and preferably suspension polymerization or emulsion polymerization, may be employed. It is generally preferred that polymerization is carried out at a temperature that ensures avoidance of degradation of all of the PVDC components, e.g., preferably from 10° C. to 120° C.; more preferably from 20° C. to 100° C.; and most preferably from 30° C. to 90° C.

Following completion of the copolymerization, the PVDC may be formed into a film or hollow fiber by any suitable method such as those known in the art. For example the PVDC may be melt-extruded, solution or latex cast in order to form the PVDC into a thin film or hollow fiber. Where films are desired, a conventionally known preparation process such as a blown film process, for example, a double bubble process or a cast film tentering process, may be especially useful to produce a biaxially oriented film. It is more preferred that a double bubble process be employed in order to concurrently extrude, biaxially orient, and anneal the PVDC film. Fibers may be produced by uniaxial stretching using known fiber processes for PVDC copolymers, and may be round or shaped hollow fibers, or of any other desired hollow fiber morphology. It is also contemplated that precursor films and/or fibers may be coextruded with multiple PVDC copolymers and/or with other polymers.

It is noted that either the film or fiber preparation process may optionally include stretching, such as stretching of the resin to form a melt-extruded film or fiber. This stretching may, in particular embodiments, be particularly effective in inducing more rapid crystallization and in increasing, and therefore improving, alignment of the PVDC crystallites. Desirably the stretch ratio ranges from 1 to 8, more desirably from 1 to 6, still more desirably from 1 to 4, and most desirably from 2 to 4.

Generally it is useful for the PVDC to have some amount of crystallinity. In the present invention this crystallinity typically ranges from 25% to 75% of the resin or formed film, as measured by differential scanning calorimetry (DSC) according to ASTM D3418. It is more preferred that this level ranges from 30% to 55%, and most preferred that this level ranges from 35% to 50%. Thus, inclusion of a comonomer generally helps to reduce precursor crystallinity to ensure the desired range, and also to reduce the melt temperature and thereby improve processability of the resulting copolymer. In general, inclusion of bulkier monomers may tend to reduce overall copolymer crystallinity by a greater amount than inclusion of less bulky monomers. Thus, for example, butyl acrylate will tend to reduce crystallinity more than, for example, methyl acrylate or ethyl acrylate, assuming such is/are used in the same mole percent (mol %) based on final copolymer composition.

To form the PVDC CMS films or hollow fibers of the present invention a pre-treatment prior to pyrolysis is employed. Generally the pre-treatment is used to stabilize, or “lock,” the copolymer structure prior to carbonization thereof. In this step the PVDC film or fiber are heated, below the melting temperature thereof (typically less than about 180° C., depending upon the exact composition of the precursor), in order to dehydrochlorinate the film to the extent of at least 10%. As used herein, the term “at least 10% dehydrochlorinated” means that the film or fiber has been pre-treated, by removing hydrogen chloride, to a point at which the PVDC copolymer film or fiber no longer melts and, in fact, begins to become infusible. It is well-accepted in the art that such a change in molecular kinetics begins to occur at a point of approximately 10% dehydrochlorination and is completed or maintained as the level of dehydrochlorination increases above that point. This step is termed a “pre-treatment” because it occurs prior to a pyrolysis step, which is the treatment step wherein carbonization is accomplished.

During the pre-treatment the copolymer structure's temperature is preferably maintained in a range of from 100° C. to 180° C., more preferably from 120° C. to 160° C., and most preferably from 130° C. to 150° C. This is preferably done in air for convenience, but other atmospheres, such as N₂ and other inert gases or oxidizing gases such as CO₂, or combinations thereof, may also or alternatively be used, since generally only minor levels of oxidation of the copolymer are anticipated within the overall given temperature range. Achievement of the desired dehydrochlorination, that is responsible for the formation of the locked structure, may be accomplished by exposure to a source of high energy irradiation, such as gamma rays, an electron beam, ultraviolet light, or a combination thereof. The time may vary from 1 hour (hr) to 48 hr, preferably from 1 hr to 24 hr, and most preferably from 1 hr to 12 hr, as needed to reach the at least 10% dehydrochlorination point, at which the copolymer begins to become infusible, i.e., no longer able to be melted. The dehydrochlorination degree can vary from 5% to 100%, depending upon pretreatment temperature and time. Where more than visual confirmation of the beginning of infusibility is desired, additional confirmation of the percentage of dehydrochlorination may be obtained by means of, for example, Thermo Gravimetric Analysis (TGA), using standard and well-known methods and equipment.

During the pre-treatment the fiber or film may be restrained to maintain its shape and preferably is. The particular restraining method may be any known in the art and may be held in tension or compression. In a particular embodiment, particularly for films, they are restrained by applying a compressive force. In particular the film is placed between two flat substrates that may be impervious to gases including the HCl being removed. Illustratively, the film may be constrained between two low surface energy plates (e.g., TEFLON plates or sheets), which are further interposed between two metal, ceramic or graphite plates. Alternatively, the plates may be pervious to gases such as the HCl being removed such as honeycomb structures. The amount of tension or compression may be any useful amount, but typically may range from 0.01 MPa to 10 MPa, from 0.1 to 1 MPa, or from 0.1 to 0.5 MPa. In the same manner, the restraining during pyrolysis may be performed in the same fashion with similar substrates, which can withstand the maximum pyrolysis temperatures used.

Following the dehydrochlorination pre-treatment, the pre-treated film or pre-treated fiber, or alternatively pre-treated CMS material, is pyrolyzed. Preferably such pyrolysis results in at least 90 wt % of the copolymer becoming carbonized, more preferably at least 95 wt %, and most preferably at least 99 wt %. As already pointed out hereinabove, this pyrolysis is also termed “carbonization,” because the result thereof is that the copolymer is converted to the carbon-only, or near carbon-only, skeleton of its copolymer structure, i.e., all or virtually all atoms other than carbon have been removed, but the carbon-carbon bonds remain substantially intact, and the CMS may now be termed to be “carbonaceous.” The pyrolysis may be carried out using any means generally known to those skilled in the art, but may be carried out at an attained maximum temperature within the range of from 350° C. to 750° C. Desirably, the temperature is at least 400° C., 450° C. to at most 700° C., 650° C., 600° C. or 550° C.

The method may form a PVDC CMS membrane that has a combination of olefin permeance and olefin/paraffin selectivity highly useful for separating the olefin from gases containing its corresponding paraffin. Such combinations generally require reasonably high olefin permeance with reasonably high selectivity or lower olefin permeance with higher selectivity.

Surprisingly, the PVDC membranes may have an average pore size that is larger than olefin desired to be separated (e.g., ethylene or propylene) and a larger gas molecule than olefin (e.g., ethane or propane) in a gas mixture. The larger gas molecule may be comprised of even larger olefins (e.g., butylene) and paraffins (e.g., butane). It is surprising, since the selectivity of ethylene/ethane or propylene/propane may be commercially useful, even though the average pore size of the membrane is larger than the larger gas molecule diameter, which would indicate that such larger gas molecule would not be preferentially rejected when flowing through the membrane (i.e., fits into the pores and would be expected to flow through the membrane). Thus, this gives rise to the belief an asymmetric structure is formed in the film as described above. In general, the average pore size of the PVDC CMS membrane at least 3 Å, 4 Å or even 5 Å to at most about 15 Å. The average pore size of the membrane may be determined by adsorption.

In addition to average micropore size, it is also often desirable in the art to optimize total micropore volume, which may be measured via the Brunauer-Emmett-Teller (BET) method at liquid N₂ temperature. Such may be further confirmed via helium (He) pycnometry and mercury (Hg) intrusion. For most separations applications, a total micropore volume of at least 0.10 mL/g, preferably at least 0.15 mL/g, more preferably at least 0.20 mL/g, according to the BET method at liquid N₂ temperature, is needed to ensure commercially efficient desirable gas adsorption.

The average micropore size and/or average micropore volume seem to suffer little, if any, alteration when additional factors, including but not limited to ramp rate to reach the attained maximum pyrolysis temperature, and/or hold time at the attained maximum pyrolysis temperature, are introduced and/or considered. For example, for industrial purposes, ramp rates ranging from 0.1° C./min to 10° C./min are typical, and hold times may range from 0 minutes (min) (i.e., ramping to the attained maximum temperature followed by immediate active or passive temperature reduction) up to 60 min (i.e., holding at the attained maximum pyrolysis temperature for up to 60 min prior to active or passive temperature reduction) are typical. The atmosphere may be any that realizes the PVDC CMS membrane. That is the atmosphere that does not substantially oxidize the PVDC and may include inert, or reducing atmospheres such as static or flowing nitrogen, inert gas (e.g., argon), carbon monoxide, hydrogen or any combination thereof.

The CMS membranes are particularly suitable for separating ethylene or propylene (olefin) in a gas feed containing its corresponding paraffin (e.g., ethane or propane) or one or more other larger gas molecules. In performing the process, the gas feed is flowed (over and through the membrane) such that a first stream (permeate) having an increased concentration of the desired olefin and second stream (retentate) having an increased concentration of the other gas molecule(s) including the desired olefin's corresponding paraffin results. When practicing the process, the CMS membrane is generally fabricated into a module comprising a sealable enclosure comprised of one or more of the carbon molecular sieve membranes described herein contained within the sealable enclosure. The sealable enclosure has an inlet for introducing a gas feed comprised of olefin and at least one other larger gas molecule; a first outlet for permitting egress of a permeate gas stream (i.e., olefin); and a second outlet for egress of a retentate gas stream (i.e., the other larger gas molecule(s)).

EXAMPLES

PVDC Copolymer Film Preparation:

Melt Extruded Films of MA 4.8 wt % Copolymer

Base PVDC copolymer with 4.8 wt % methyl acrylate (MA) comonomer (named as MA4.8 wt %, Mw=96,000, The Dow Chemical Company, Midland, Mich.) was blended with 2 wt % epoxidized soybean oil (based on total amount of blend), 4 wt % dibutyl sebacate, and 2 wt % PLASTISTRENGTH L-1000 an acrylic lubricant available from Arkema PLC, France. The blend was extruded through a 1.75 inch width film die (controlled at 174° C.) followed by water quench and stretch winding. The wind rate was controlled to obtain films of 2 mil (1 mil=25.4 micrometer). The films after winding were cut into approximately 12 inch wide and 2 feet length pieces and laid on flat desktop for about one week. Coupons of ⅞ inch diameter were cut for carbonization as described below.

Melt Extruded Films of MA 8.5 wt % Copolymer

PVDC copolymer with 8.5 wt % methyl acrylate comonomer (named as MA8.5 wt %, Mw=85,000, The Dow Chemical Company) was blended with 2 wt % epoxidized soybean oil and 2 wt % PLASTISTRENGTH L-1000. The blend was extruded in the same manner as above. The wind rate was controlled to obtain films that are 2 mil (˜50 micrometers) thick. The films after winding were cut into approximately 12 inch wide and 2 feet length pieces and laid on flat desktop for about one week.

Melt Bubble Extruded Films of MA 4.8 wt % Copolymer

Base PVDC copolymer with 4.8 wt % methyl acrylate (MA) comonomer (named as MA4.8 wt %, Mw=96,000, The Dow Chemical Company, Midland, Mich.) was blended with 2 wt % epoxidized soybean oil (based on total amount of blend), 4 wt % dibutyl sebacate, and 2 wt % PLASTISTRENGTH L-1000 an acrylic lubricant available from Arkema PLC, France. The resin was melt extruded using a commercial bubble extruder to form films having a thickness of 0.4 mil (˜10 micrometers).

Melt Bubble Extruded Films of VC17.6 wt % Copolymer

PVDC copolymer with 17.6 wt % vinyl chloride (VC) comonomer (named as VC17.6 wt %, The Dow Chemical Company) was blended with 2 wt % epoxidized soybean oil and 2 wt % PLASTISTRENGTH L-1000. The resin was melt extruded using a commercial bubble extruder to form films having a thickness of 0.4 mil (˜10 micrometers).

TABLE 1 Precursor Films Precursor Film thickness Film # Preparation method Base resin [mil] 1 Melt extrusion MA4.8 wt % 2 2 Melt extrusion MA8.5 wt % 2 3 Bubble Melt extrusion MA4.8 wt % 0.4 4 Bubble Melt extrusion VC17.6 wt % 0.4 Carbon Membrane Formation

A two-step pyrolysis approach was used. The precursor films were heated to a first temperature of 130-150° C. for 24 hours in a low temperature oven purged by 2 L/min of air (pretreated films), which was followed by further heating to pyrolyze the pretreated films to temperatures in the range of 350-950° C. in a 6″ ID quartz tube furnace purged by 5 L/min of nitrogen.

For the initial low temperature pretreatment, 12 disks (⅞ inch diameter) sandwiched between porous ceramic honeycomb plates, through which HCl generated should be transported out swiftly. A scrubber connected to this oven contained a 10 wt % sodium hydroxide aqueous solution. A loaded oven was heated at 1° C./min to the temperature shown in Table 2 (Pretreatment Temperature) and held for 24 hours under 2 L/min of air purge.

For the second heating step, the 12 pretreated disks were sandwiched between the porous ceramic honeycomb plates were loaded into a 6″ ID quartz tube furnace. A scrubber connected to this furnace contained a 10 wt % sodium hydroxide aqueous solution. The furnace was raised to 500° C. at 3° C./min), and held for 30 minutes at the final temperature and then cooled down to room temperature (˜25° C.). After cooling down, the carbon membranes were put into a storage box continuously purged with dry nitrogen at a flow rate of 5 Liter/min.

Carbon Membrane Permeation Test

The carbon membranes were masked onto a standard 25 mm filter holder (Millipore #4502500, EMD Millipore Corp., Germany) using an impermeable aluminum tape, leaving an open defined permeation area. A two-part epoxy (J-B Weld twin tube) was then applied along the interface of the tape and the carbon membranes. Mixed permeation tests of several gas species were conducted at 20° C. with a continuous upstream feed of either an equimolar mixture of H₂/CO₂/CH₄ (total 75 sccm, 1 atm) or an equimolar mixture of C₂H₄/C₂H₆/C₃H₆/C₃H₈ (total 50 sccm, 1 atm), and downstream He purge (2.0 sccm, 1 atm). The permeate carried by the He purge gas was analyzed by a GC (gas chromatograph) with a TCD (thermal conductivity detector for H₂ and CO₂) and FID (flame ionization detector for all the hydrocarbons). The concentrations in all gases were lower than 5%, so the gas flow rate in downstream was considered the same as the He flow rate. The membrane permeate rate was calculated using the He purge flow rate times the permeate concentrations measured by GC. The tests were run for several hours to days until the permeate concentrations were steady. The parameters to make the carbon membranes are shown in Table 2. The resulting permeation results are shown in Table 3.

TABLE 2 CMS film Pre-treatment Temp. Final Pyrolysis Temp. Precursor Example [° C.] [° C.] * film # Ex. 1 130 500 3 Ex. 2 130 500 4 Comp. Ex 1 130 500 1 Comp. Ex. 2 130 500 2

TABLE 3 Ethylene/ Propylene/ Hydrogen Methane Ethylene Ethane Propylene Propane ethane propane CMS film Permeance Permeance H₂/CH₄ Permeance Permeance Permeance Permeance selectivity selectivity Ex. (GPU) (GPU) Selectivity (GPU) (GPU) (GPU) (GPU) [—] [—] Ex. 1 132 1.76 75 3.30 0.92 2.14 0.09 3.6 23.5 Ex. 2 133 1.47 90 2.66 0.70 1.43 0.03 3.8 51.1 Comp. Ex. 1 96 0.28 343 0.59 0.10 0.24 BDL 6.1 N/A Comp. Ex. 2 83 0.53 156 1.05 0.17 0.42 BDL 6.3 N/A

Comp. Ex.1 and Comp. Ex.2 are highly selective CMS membrane for H₂/CH₄ separation. However, the flux (permeance) of hydrocarbon molecules are too small, particularly ethylene and propylene which have a permeance lower than ˜1GPU, making them not useful industrially.

Ex.1 and Ex.2 were made essentially the same as Comp. Ex. 1 and Ex. 2 respectively but were much thinner (˜50 micrometers versus ˜10 micrometers). The thinner CMS films of Ex.1 and Ex.2 had substantially worse H₂/CH₄ selectivities, making them unattractive for that application anymore. However, the fluxes of ethylene and propylene increased to industrially useful ranges (>1 GPU at 20° C.) for olefin/paraffin separations and displayed useful olefin/paraffin selectivities. 

The invention claimed is:
 1. A method of making a carbonized polyvinylidene chloride copolymer useful to separate an olefin from its corresponding paraffin comprising, (a) providing a polyvinylidene chloride copolymer film or hollow fiber having a thickness of 1 micrometer to 20 micrometers, (b) heating the polyvinylidene chloride copolymer film or hollow fiber to a pretreatment temperature of 100° C. to 180° C. while restraining the polyvinylidene chloride copolymer film or hollow fiber by applying a force to form a pretreated polyvinylidene chloride copolymer film or hollow fiber, and (c) heating the pretreated polyvinylidene chloride copolymer film or hollow fiber to a maximum pyrolysis temperature from 350° C. to 750° C. while restraining the pretreated polyvinylidene chloride copolymer film or hollow fiber by applying a force; wherein the polyvinylidene chloride copolymer film or hollow fiber is formed by melt-extrusion at a stretch ratio from 1 to
 8. 2. The method of claim 1, wherein the maximum pyrolysis temperature is at most 650° C.
 3. The method of claim 1, wherein the polyvinylidene chloride copolymer film or hollow fiber is a polyvinylidene chloride copolymer comprised of vinylidene chloride and at least one of the following: a vinyl monomer; a vinyl chloride monomer; an acrylate monomer; a methacrylate monomer; a styrenic monomer; acrylonitrile, methacrylonitrile; itaconic acid; chlorotrifluoroethylene that have been copolymerized.
 4. The method of claim 1, wherein the thickness is from 1 micrometers to 10 micrometers.
 5. A process for separating an olefin from a gas mixture having the olefin's corresponding paraffin, the process comprising (i) providing a carbonized polyvinylidene chloride copolymer membrane having a thickness of 1 micrometer to 20 micrometers and an average pore size greater than the olefin or paraffin as determined by gas permeation employing gas probe molecules of differing sizes; and (ii) flowing the gas mixture through said carbonized polyvinylidene chloride copolymer membrane to produce a permeate first stream having an increased concentration of the olefin and a second retentate stream having an increased concentration of its corresponding paraffin.
 6. The process of claim 5, wherein the olefin is ethylene or propylene.
 7. The process of claim 6, wherein the paraffin is ethane or propane.
 8. The process of claim 5, wherein the average pore size is greater than 4 angstroms.
 9. The process of claim 8, wherein the average pore size is greater than 5 angstroms. 